JP3518794B2 - Polyolefin-based colored resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyolefin-based colored resin composition, and more particularly to a polyolefin-based colored resin composition capable of effectively suppressing the generation of eyelids (die-cass) due to a pigment during molding. It is about.

[0002]

2. Description of the Related Art Conventionally, when molding a polyolefin-based colored resin composition containing a pigment, at the tip of a molding machine such as an extruder die or an inflation lip, as the processing time elapses, the resin composition residue It is known that (hereinafter referred to as “meyani”) adheres. When such a body is generated, an unfavorable situation is brought about such as streaking in the molded product or foreign matter caused by mixing of the body, which causes a problem that the product value is unavoidable.
Therefore, if the cleaning of the molding machine is carried out in order to remove the eyelid from the die or the lip, it causes a decrease in productivity.Therefore, in general, a commercially available eyelid inhibitor or a high eyelid inhibitor is used. The fact is that the use of a resin composition blended in a concentration is used to prevent the eye damage. In general, conventional anti-meyer agents mainly consist of (1) those containing silica, talc, calcium carbonate and other inorganic oxide powders as main components, and (2) metal soaps, fluorine-based lubricants and lubricants such as fatty acid amides. It can be roughly divided into what is used as an ingredient. When the inorganic oxide powder of the above (1) is blended with the resin composition to give the anti-eye effect, a particle size of about 0.1 to 10 μm is generally used, but a large anti-eye effect is obtained. In addition, there is a problem that particles are aggregated and foreign matters having a particle diameter of about 20 to 100 μm are easily generated. On the other hand, when the above-mentioned lubricant (2) is added to the resin composition to give the anti-eye effect, a considerable anti-eye effect is obtained and the above-mentioned foreign matter is not generated.

Typical examples of this lubricant type anti-meyer agent include zinc stearate, fluoroelastomer, polytetrafluoroethylene powder, oleic acid amide, ethylene bis-stearic acid amide, etc. The effect will be described below. First, a metal soap such as zinc stearate has a polarity between resin and pigment and has high compatibility with both. Therefore, when used as an anti-meyer agent, because of this high compatibility, it is uniformly dispersed inside the resin, and the effective zinc concentration of zinc stearate is small on the surface of the resin composition, which is the location where the melanis occur. The amount of addition necessary for the prevention effect increases, and as a result, there arise problems such that physical properties are adversely affected and cost increase is inevitable. As one kind of metal soap, magnesium hydroxystearate is known, but it is difficult to disperse itself, and it is difficult to use it as an anti-meyer agent. Next, a self-lubricating material having a small friction coefficient such as a fluoroelastomer or a polytetrafluoroethylene powder, which is a fluorine-based lubricant, is not compatible with a polyolefin, and thus it is difficult to disperse the resin composition in the resin composition. On the surface, the percentage that can be effectively used is low. However, the melt viscosity of the fluorine-based lubricant is higher than that of the polyolefin (at the processing temperature of about 130 to 300 ° C). Further, as described above, the fluorine resin may not have good compatibility with the polyolefin, so that a very large shearing force is required to uniformly disperse the fluorine lubricant in the polyolefin. If a shearing force for sufficient dispersion cannot be obtained, there is a problem that the effect of preventing eye damage is not sufficiently exhibited. Furthermore, fatty acid amide lubricants such as oleic acid amide and ethylenebisstearic acid amide are
The compatibility is intermediate between the above-listed lubricants, and the proportion available on the surface of the resin composition is higher than that of the metal soap, but this amide lubricant is also almost uniform when the resin composition is melted. However, there is a problem in that the contribution to the eye damage prevention effect is not so large. Thus, with respect to the polyolefin-based colored resin composition containing the pigment, the anti-meyer agent that can sufficiently impart the anti-eye effect is the fact that it has not been found so far,
There has been a demand for the development of a polyolefin-based colored resin composition that is excellent in the prevention of eye damage.

[0004]

Under the above circumstances, the present invention provides a polyolefin-based colored resin composition which can effectively suppress the generation of eye drops (die residue) due to the pigment during molding. It was made for the purpose of providing.

[0005]

Means for Solving the Problems The inventors of the present invention have earnestly studied to develop a polyolefin-based colored resin composition having excellent methine-proof property, and have obtained the following findings. Organic compounds having a hydroxyl group, for example, alcohols such as polyethylene glycol and polypropylene glycol, hydroxy fatty acids, hydroxy fatty acid metal salts, hydroxy fatty acid esters, and hydroxy fatty acid amides are compounds whose adsorption to a metal by a hydroxyl group is remarkable. , When using these compounds, a thin film is formed on the machine wall of the processing machine, its internal screw, etc., and it is revealed by various experiments that the thin film has the effect of preventing the eye stain of the colored resin composition. It was Of these, alcohols and hydroxy fatty acids are water-soluble or hydrophilic, are not compatible with polyolefin-based resins, and form a hydroxy compound-rich crystal part, which becomes a foreign substance, and is therefore suitable for use. Moreover, it was found that the hydroxy fatty acid metal salts have good compatibility with the polyolefin resin and are easy to process, but the thin film forming effect is weakened by the polarity of the metal salt, and the dent prevention effect is not sufficient. Furthermore, in the case of hydroxy fatty acid esters, the lipophilicity is strong and the film thickness of the thin film layer becomes thin, and the effect of preventing eye drop is insufficient, but in the case of hydroxy fatty acid amides, the thin film layer is thick and the effect of preventing eye drop is the best. It was found that there was no problem in workability. The present inventors, as a result of further research based on the above findings, a resin composition obtained by mixing a pigment and a hydroxy fatty acid amide in a predetermined ratio with respect to a polyolefin resin, at the time of molding,
It has been found that the generation of porcelain can be effectively suppressed, and the workability and the physical properties of molded articles thereof are good. The present invention has been completed based on such findings.

That is, according to the present invention, (1) 100 parts by weight of a polyolefin resin (A) is used, and (B) a pigment of 0.1 part is added.
The present invention provides a polyolefin-based colored resin composition, which comprises 0.1 to 200 parts by weight and 0.01 to 10 parts by weight of (C) hydroxy fatty acid amide.
Further, in a preferred aspect of the present invention, the hydroxy fatty acid amide of the component (2) (C) has 8 carbon atoms of the hydroxy fatty acid.
To 22. The polyolefin-based colored resin composition according to item (1), and (3) the hydroxy fatty acid amide according to item (2), wherein the hydroxy fatty acid has 18 carbon atoms. A composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the polyolefin-based colored resin composition of the present invention, the polyolefin-based resin used as the component (A) is not particularly limited and includes, for example, ethylene, propylene, butene-1,3-methylbutene-
1,3-methylpentene-1,4-methylpentene-1
Α-olefin homopolymers and copolymers thereof, and copolymers of these with other copolymerizable unsaturated monomers. As typical examples, high density, medium density, low density polyethylene and linear low density polyethylene, polyethylenes such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, propylene homopolymer, propylene- Polypropylenes such as ethylene block copolymers, random copolymers, propylene-ethylene-diene compound copolymers, polybutyne-
1, poly 4-methyl pentene-1 etc. can be mentioned. These polyolefin resins may be used alone or in combination of two or more. Also,
The pigment used as the component (B) is not particularly limited, and any known inorganic pigment or organic pigment conventionally used as a pigment for plastics can be appropriately selected and used. Here, examples of the inorganic pigment include titanium oxide, carbon black, iron oxide, yellow lead, titanium yellow, ultramarine blue, aluminum pigment, pearl pigment, and calcined pigment, while examples of the organic pigment include
Examples thereof include azo pigments, nitroso pigments, nitro pigments, basic dye lakes, acid dye lakes, mordant dye lakes, vat dye pigments, phthalocyanine pigments, and quinacridone pigments.

In the present invention, the pigment as the component (B) may be used alone or in combination of two or more kinds. The blending amount is selected within the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the polyolefin resin as the component (A). If the blending amount is less than 0.01 parts by weight, the coloring effect is not sufficiently exerted, and if it exceeds 200 parts by weight, the increase in coloring is not recognized for the amount,
Rather, it is economically disadvantageous and the physical properties of the resulting molded article may deteriorate. Considering the coloring effect, the physical properties of the molded article, the economical efficiency, etc., the preferable blending amount of the component (B) is in the range of 0.1 to 120 parts by weight.

On the other hand, the hydroxy fatty acid amide used as the component (C) is not particularly limited and may be appropriately selected and used from various compounds such as monoamide and bisamide according to various situations. , Those in which the carbon number of the hydroxy fatty acid moiety is in the range of 8 to 22 are preferable, and in particular, from the viewpoint of easy availability and effect,
Those having 18 carbon atoms are preferable. The hydroxy fatty acid moiety may be either saturated fatty acid or unsaturated fatty acid. Specific examples of the hydroxy fatty acid amide include hydroxy stearic acid amide, ricinoleic acid amide, ethylene bis hydroxy stearic acid amide, and hexamethylene bis hydroxy stearic acid amide. In the present invention, the hydroxy fatty acid amide as the component (C) may be used alone or in combination of two or more. Further, the blending amount is 0.01 to 100 parts by weight of the polyolefin resin as the component (A).
It is selected in the range of 10 parts by weight. If the blending amount is less than 0.01 part by weight, the effect of preventing mingling is not sufficiently exerted,
If it exceeds 10 parts by weight, the workability is significantly reduced. From the standpoint of balance between the effect of preventing edging and the processability, the preferable blending amount of this component (C) is in the range of 0.01 to 5.0 parts by weight, particularly in the range of 0.05 to 1.0 parts by weight. Is preferred.

To the polyolefin-based colored resin composition of the present invention, an anti-inking agent other than the above-mentioned hydroxy fatty acid amide, such as metal soap, may be added, if desired, within a range not impairing the object of the present invention. The polarity may be changed to improve the anti-meyer effect, and further, various known addition components conventionally used in polyolefin resin compositions, specifically, antioxidants, heat stabilizers, and ultraviolet rays. Absorbers, light stabilizers, various fillers, reinforcing materials,
A flame retardant, a release agent, an antistatic agent, etc. may be contained,
Further, other thermoplastic resin may be contained. The method for preparing the colored resin composition is not particularly limited, and is a conventionally known method, for example, the above-mentioned component (A), component (B), (C).
A method of mixing the components and various additives used as desired with a mixer such as a V-type blender, a ribbon blender, or a Henschel mixer, or a method of kneading with a kneader such as an extruder, a mixing roll, a Banbury mixer, or a kneader. Alternatively, a method of mixing and kneading by combining a mixer and a kneader can be used. The polyolefin-based colored resin composition of the present invention thus obtained can be processed into a desired molded article by various known molding methods such as injection molding, extrusion molding, and inflation molding.

[0011]

[Function] The cause of the occurrence of mesiness at the time of molding a colored resin composition containing a pigment is due to the pigment in the composition.
It is considered that this is due to the decrease in slipperiness and the generation of frictional heat due to the friction (shear stress) between the machine wall and the molten resin. The polyolefin-based colored resin composition of the present invention contains a hydroxy fatty acid amide, and since the hydroxy fatty acid amide has a hydroxyl group, it is adsorbed to the machine wall to form a thin film, and the thin film forms a thin film with the machine wall. It is presumed that the friction with the molten resin is reduced and the cushioning effect is exerted, and as a result, the occurrence of mesiness in the colored resin composition is prevented.

[0012]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the reduction rate of the resin composition was calculated by the following method. <Mayney reduction rate of resin composition> W ₂ is the amount (g) of the colored resin composition containing the anti-inking agent, and W ₁ is the amount of the colored resin composition (g) that does not contain the anti-inking agent. Using the following formula, the reduction rate (%) is calculated. Meaning reduction rate (%) = [(W ₁ −W ₂ ) / W ₁ ] × 100 Meaning reduction rate of 80% or more was passed, and less than 80% was rejected. Example 1 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 minutes) 0.5 parts by weight of ethylenebishydroxystearic acid amide and 5 parts by weight of titanium dioxide were mixed with 100 parts by weight, and then continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin. A composition was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 2 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.3 g / 10 min) 100 parts by weight, 0.04 parts by weight of ethylenebishydroxystearic acid amide and 3 parts by weight of aluminum pigment were blended, and then continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin. A composition was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 3 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight of ethylenebishydroxystearic acid amide (0.05 parts by weight) and carbon black (5 parts by weight) were blended, and then continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin. A composition was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 4 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight were mixed with 0.05 parts by weight of ethylenebishydroxystearic acid amide and 5 parts by weight of ultramarine blue, followed by continuous operation with a φ30 mm single screw extruder to give 5 kg of a colored resin composition. The product was prepared, and the rate of decrease in body loss was calculated. The results are shown in Table 1.

Example 5 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight of ethylene bishydroxystearic acid amide (0.05 parts by weight) and cyanine blue (5 parts by weight) were mixed, and then continuously operated with a φ30 mm single screw extruder to obtain 5 kg of colored resin. A composition was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 6 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight of ethylene bishydroxystearic acid amide (0.05 parts by weight) and cyanine green (5 parts by weight) were mixed, and continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin. A composition was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 7 High density polyethylene (average density 0.96 g / cm ³ , MFR
(0.05 g / 10 min) 100 parts by weight of ethylene bishydroxystearic acid amide (0.05 parts by weight) and aluminum pigment (4 parts by weight) were mixed, and continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin. Prepare a composition,
The reduction rate of the body loss was calculated. The results are shown in Table 1. Example 8 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight, ethylene bishydroxystearic acid amide 0.3 parts by weight, magnesium stearate 0.2 parts by weight and titanium dioxide 5 parts by weight were mixed, and then, using a φ30 mm single screw extruder. Continuous operation,
A colored resin composition of 5 kg was prepared, and the rate of decrease in porcelain was determined. The results are shown in Table 1. Example 9 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight of hydroxystearic acid amide (0.04 parts by weight) and aluminum pigment (3 parts by weight) were mixed, and then continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin composition. Was prepared, and the rate of decrease in porcelain was obtained. The results are shown in Table 1.

Comparative Example 1 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.3 g / 10 minutes) 1 part by weight of zinc stearate and 5 parts by weight of titanium dioxide were mixed with 100 parts by weight, and then φ3
Continuous operation was carried out with a 0 mm single-screw extruder to prepare 5 kg of a colored resin composition, and the reduction rate of the ink drop was determined. The result is first
Shown in the table. Comparative Example 2 Low density polyethylene (average density 0.92 g / cm ³ , MFR
(0.3 g / 10 min) 100 parts by weight of zinc stearate (0.05 parts by weight) and titanium dioxide (5 parts by weight) were mixed, and then continuously operated with a φ30 mm single screw extruder to obtain 5 kg of the colored resin composition. After preparation, the rate of decrease in porridge was determined. The results are shown in Table 1. Comparative Example 3 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.3 g / 10 min) 100 parts by weight were mixed with 1 part by weight of 12-hydroxymagnesium stearate and 5 parts by weight of titanium dioxide, and then continuously operated with a φ30 mm single screw extruder to give 5 kg of the colored resin composition. Was prepared, and the rate of decrease in porcelain was obtained. The results are shown in Table 1. Comparative Example 4 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.5 g of hydroxystearic acid and 5 parts by weight of titanium dioxide were mixed with 100 parts by weight of 0.3 g / 10 minutes), and then continuously operated with a φ30 mm single screw extruder to obtain 5 kg of the colored resin composition. After preparation, the rate of decrease in porridge was determined. The results are shown in Table 1. Comparative Example 5 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.5 g of ethylenebisstearic acid amide and 5 parts by weight of titanium dioxide were mixed with 100 parts by weight of 0.3 g / 10 minutes), and then continuously operated with a φ30 mm single screw extruder to give 5 kg of a colored resin composition. The product was prepared, and the rate of decrease in body loss was calculated. The results are shown in Table 1.

[0015]

[Table 1]

[Note] (1) The parts by weight of the anti-meyer agent and the pigment are values based on 100 parts by weight of the resin. (2) In Example 7, high-density polyethylene (average density of 0.
96 g / cm ³ , MFR 0.05 g / 10 minutes). (3) Except for Example 7, low density polyethylene (average density 0.92 g / cm ³ , MFR 0.3 g / 10 min) is used.

As can be seen from Table 1, the colored resin composition of the present invention containing hydroxy fatty acid amide (Example 1
Nos. 9 to 9) were 8 to 99.4% of the various pigments, and the porcelain reduction rate was good, and the porridge prevention effect was good.
On the other hand, Comparative Examples 1 to 5 containing other anti-meyer agents
In all cases, the reduction rate of the eyelid was less than 80%, and the eyelid prevention effect was insufficient. Test Example 1 Low density polyethylene (average density 0.92 g / cm ³ , MFR
0.5 g by weight of titanium dioxide and 0.05 part by weight of ethylenebishydroxystearic acid amide per 100 parts by weight of a single screw extruder (C1 to H = 160 ° C.).
Were melt-dispersed in to prepare pellets having a size of 3 × 3 mm. For comparison, 5 parts by weight of titanium dioxide was melt-dispersed with a single screw extruder (C1 to H = 160 ° C.) to 100 parts by weight of the same low-density polyethylene as described above, and a size of 3 was obtained.
Standard pellets of x3 mm were prepared. Next, using the above pellets, an inflation molding machine (C1 to H = 150
At 20 ° C., a colored film having a thickness of 20 μm was produced, and the physical properties of the film were determined according to the following methods. (1) 10 with each film having dispersibility of 1000 cm ^2.
The foreign matter having a size of 0 μm or more was measured. The results are shown in Table 2. (2) Using each film having a color tone of 1000 cm ² , a color tone comparison test with a standard film was performed. The results are shown in Table 2. (3) Transmittance The infrared spectroscopy spectrum of each film was measured, the transmittance was obtained, and comparative evaluation with the standard film was performed. The results are shown in Table 2. (4) Tensile Strength and Tensile Elongation Regarding each film, according to JIS K 7113,
Tensile strength and tensile elongation were measured. The results are shown in Table 2. (5) Heat sealability Heat sealer (trade name: Hand Sealer HS-BE, manufactured by New Long Co., Ltd.) using 2 sheets of each film
At 150 ° C., a heat seal test was performed. The results are shown in Table 2. (6) Printability Each film was printed with yellow, red, indigo, and black ink, and the ink peeling test with cellophane tape and the ink rub resistance test with Gakushin type rub fastness tester were performed. . The results are shown in Table 2.

[0018]

[Table 2]

As is clear from Table 2, the film obtained from the colored resin composition of the present invention has various physical properties.
It turns out that there is no problem at all.

[0020]

INDUSTRIAL APPLICABILITY The polyolefin-based colored resin composition of the present invention can effectively suppress the generation of dents (die-casses) due to the pigment during molding, and therefore can give various molded products of good quality. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-52-71546 (JP, A) JP-B 47-4136 (JP, B1) JP-B 44-7528 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. A blend of 0.01 to 200 parts by weight of a pigment (B) and 0.01 to 10 parts by weight of a hydroxy fatty acid amide (C) with respect to 100 parts by weight of a polyolefin resin (A). A polyolefin-based colored resin composition which is used. 2. The hydroxy fatty acid amide of the component (C) is
The polyolefin-based colored resin composition according to claim 1, wherein the hydroxy fatty acid has 8 to 22 carbon atoms.